Synthesis and characterization of M<Subscript>3</Subscript>V<Subscript>2</Subscript>O<Subscript>8</Subscript> (M = Ca,Sr and Ba) by a solid-state metathesis approach

A solid-state metathesis approach initiated by microwave energy has been successfully applied for the synthesis of orthovanadates, M₃V₂O₈ (M = Ca, Sr, and Ba). The structural, vibrational, thermal, optical and chemical properties of synthesized powders are determined by powder X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, magnetic property measurements and diffused reflectance spectra in the UV-VIS range. The direct bandgap of the synthesized materials was found to be 3·55 ± 0·2 eV, 3·75 ± 0·2 eV and 3·57 ± 0·2 eV for Ca₃V₂O₈, Sr₃V₂O₈ and Ba₃V₂O₈, respectively.     

Synthesis and dielectric properties of a new class of MX6Ti6O19 (M=Ba,Sr and Ca; X=Mg and Zn) ceramics

MX₆Ti₆O₁₉ (M=Ba, Sr and Ca; X=Mg and Zn) ceramics have been synthesized by the conventional solid state ceramic route. The dielectric properties such as dielectric constant (ε_r), loss tangent (tanδ) and temperature coefficient of dielectric constant (τ_εr) of the sintered ceramic compacts are studied using an impedance analyzer up to the 13-MHz region. The zinc compositions have relatively high dielectric constant and low loss tangent compared to the Mg analogue. Out of the samples studied, BaZn₆Ti₆O₁₉ ceramics show excellent dielectric properties. The structure and microstructure of these ceramic samples are also studied using powder X-ray diffraction, FTIR and SEM methods, and the results are presented.     

Synthesis of nanocomposites based on MO-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> (M = Ca,Sr, Ba) glasses

This work examines the effect of KBF₄ additions on the crystallization behavior of glasses based on the multicomponent systems MO-Bi₂O₃-B₂O₃ with M = Ca, Sr, and Ba. The glass-ceramic composites obtained contain a δ-Bi₂O₃-based crystalline phase with a crystallite size of ≃7 nm, evenly distributed over the glass matrix. The 400°C electrical conductivity of the nanocomposites reaches 2 × 10⁻⁴ S/cm, and the activation energy is 1.1 eV, typical of anion conduction. These values are comparable to those reported for δ-Bi₂O₃ ceramics.     

Synthesis of Ba<Subscript>3</Subscript>ZnNb<Subscript>2</Subscript>O<Subscript>9</Subscript>−Sr<Subscript>3</Subscript>ZnNb<Subscript>2</Subscript>O<Subscript>9</Subscript> solid solution and their dielectric properties

Oxides of the type, Ba_3-xSr_xZnNb₂O₉ (0 ≤x ≤3), were synthesized by the solid state route. Oxides calcined at 1000°C show single cubic phase for all the compositions. The cubic lattice parameter (a) decreases with increase in Sr concentration from 4.0938(2) forx = 0 to 4.0067(2) forx = 3. Scanning electron micrographs show maximum grain size for thex = 1 composition (∼ 2 μm) at 1200°C. Disks sintered at 1200°C show dielectric constant variation between 28 and 40 (at 500 kHz) for different values of x with the maximum dielectric constant atx = 1.     

Comparative study of dielectric properties of MgNb<Subscript>2</Subscript>O<Subscript>6</Subscript> prepared by molten salt and ceramic method

Magnesium niobate (MgNb₂O₆) powder was synthesized by the conventional ceramic route as well as by the molten salt route using a eutectic mixture of NaCl-KCl as the salt and Mg(NO₃)₂-6H₂O and TiO₂ as the starting materials. Pure phase of MgNb₂O₆ could be obtained by the molten salt method at 1100°C. However, in ceramic method the pure phase of MgNb₂O₆ was obtained by heating at 1025°C for 20 h. On sintering at 1100°C the dielectric constant and dielectric loss of MgNb₂O₆ obtained by the molten salt method was found to be 19.5 and 0.004 at 100 kHz at room temperature. Lower values were obtained for these oxides prepared by the ceramic route, 16.6 and 0.000518, respectively. In both cases the dielectric constant was quite stable with frequency.     

Effect of Pb(Ti,Sn)O<Subscript>3</Subscript> on the dielectric properties of high dielectric constant X8R BaTiO<Subscript>3</Subscript>-based ceramics

The high dielectric constant X8R dielectric materials could be sintered at 1,240 °C by doping 2.5 mol% Pb(Ti,Sn)O₃ additives into the BaTiO₃ ceramics, with a dielectric constant greater than 3,400 at 25 °C, dielectric loss lower than 2.0% and temperature coefficient of capacitance (TCC) less than ±15% from −55 to 150 °C, which satisfied X8R specification. The effects of Pb(Ti,Sn)O₃ on the microstructure and dielectric properties of BaTiO₃-based ceramics were investigated. Doped with Pb(Ti,Sn)O₃ additives, the partial solid solution was formed between Pb(Ti,Sn)O₃ and BaTiO₃. Due to the high Curie point of Pb(Ti,Sn)O₃, the Curie point of the ceramics was markedly shifted to higher temperature about 150 °C, and the temperature coefficient of capacitance curves was flattened. The increase of the tetragonality (c/a ratio) and the fine microstructure were resulted in the increase of dielectric constant. With Pb(Ti, Sn)O₃ content up to 3 mol%, the depression of Ti⁴⁺’s polarization and the decrease of the tetragonality (c/a ratio) were resulted in the decrease of dielectric constant.     

Dy<Superscript>3+</Superscript>-activated M<Subscript>2</Subscript>SiO<Subscript>4</Subscript> (M = Ba,Mg, Sr)-type phosphors

The alkaline orthosilicates of M₂SiO₄ (M = Ba, Mg, Sr) activated with Dy³⁺ and co-doped with Ho³⁺ are prepared through conventional solid-state method, i.e., mixing and grinding of solid form precursors followed by high-temperature heat treatments of several hours in furnaces, generally under open atmosphere and investigated by X-ray diffraction (XRD) to get phase properties and photoluminescence (PL) analysis to get luminescence properties. The thermal behaviours of well-mixed samples were determined by differential thermal analysis (DTA)/thermogravimetry (TG). The PL spectra show that the 478 and 572 nm maximum emission bands are attributed, respectively, to ⁴F_9/2 → ⁶H_15/2 and ⁴F_9/2 → ⁶H_13/2 transitions of Dy³⁺ ions.     

Luminescence of Pb<Superscript>2+</Superscript> in MAl<Subscript>2</Subscript>B<Subscript>2</Subscript>O<Subscript>7</Subscript> (M = Ca,Sr)

Pb²⁺ doped SrAl₂B₂O₇ was prepared by solution combustion synthesis. The synthesized material was determined by powder XRD. The photoluminescence properties of the synthesized phosphor were investigated at room temperature using a spectrofluorometer. The emission peak of Pb²⁺ doped SrAl₂B₂O₇ was observed at 420 nm upon excitation at 277 nm. The Stokes shift of SrAl₂B₂O₇:Pb²⁺ was calculated to be 12 292 cm⁻¹. The luminescence behavior of Pb²⁺ in both SrAl₂B₂O₇ and CaAl₂B₂O₇ was discussed. The text was submitted by the authors in English.     

Synthesis and high-temperature electrical conductivity of Ln<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript> and LnYTi<Subscript>2</Subscript>O<Subscript>7</Subscript> (Ln = Dy,Ho)

Ho₂Ti₂O₇ and LnYTi₂O₇ (Ln = Dy, Ho) pyrochlores have been synthesized using hydroxide coprecipitation, mechanical activation, and firing at 1600°C. The bulk and grain-boundary components of their conductivity have been determined for the first time by impedance spectroscopy. The 740°C bulk conductivity of Ho₂Ti₂O₇ is 4 × 10^?4 S/cm, and that of HoYTi₂O₇ is 1 × 10^?3 S/cm, with activation energies E _a = 1.01 and 1.17 eV, respectively, suggesting that these materials are new oxygen-ion conductors. The bulk conductivity of DyYTi₂O₇ (3 × 10^?4 S/cm at 740°C, E _a = 1.09 eV) is almost one order of magnitude lower than that of HoYTi₂O₇ (1 × 10^?3 S/cm at 740°C, E _a = 1.17 eV).     

Thermochemical and luminescent properties of the K<Subscript>2</Subscript>MgV<Subscript>2</Subscript>O<Subscript>7</Subscript> and M<Subscript>2</Subscript>CaV<Subscript>2</Subscript>O<Subscript>7</Subscript> (M = K,Rb, Cs) vanadates

We have studied the compounds K₂MgV₂O₇ and M₂CaV₂O₇ with M = K, Rb, and Cs. These vanadates melt incongruently in the range 635–717°C. Cooling their decomposition products to room temperature leads to the formation of nonequilibrium phase assemblages characteristic of the corresponding oxide systems. The compounds offer broadband photo- and radioluminescence with an essentially white (to the human eye) emission spectrum. A model is proposed for luminescence centers in the vanadates, which involves the formation of defects in vanadium-oxygen groups, and an energy level diagram of the emission centers is constructed in the form of configuration curves in the harmonic oscillator approximation. The luminescent properties of these compounds suggest that they can be used as basic components of cathodo- and roentgenoluminescent screens and white-light-emitting diodes with improved color performance.     

Low temperature sintering and microwave dielectric properties of Li<Subscript>6</Subscript>Mg<Subscript>7</Subscript>Ti<Subscript>3</Subscript>O<Subscript>16</Subscript> ceramics with LiF additive for LTCC applications

Li₆Mg₇Ti₃O₁₆ ceramics were prepared by the conventional solid-state method with 1–5 wt% LiF as the sintering aid. Effects of LiF additions on the phase compositions, sintering characteristics, micro-structures and microwave dielectric properties of Li₆Mg₇Ti₃O₁₆ ceramics were investigated. The LiF addition could effectively lower the sintering temperature of Li₆Mg₇Ti₃O₁₆ ceramics from 1550 to 900 °C. For different LiF-doped compositions, the optimum dielectric permittivity (ε _r ) and quality factor (Q·f) values first increased and then decreased with the increase of LiF contents, whereas the temperature coefficient of resonant frequency (τ _f ) fluctuated between ??14.39 and ??8.21 ppm/°C. Typically, Li₆Mg₇Ti₃O₁₆ ceramics with 4 wt% LiF sintered at 900 °C exhibited excellent microwave dielectric properties of ε _r ?=?16.17, Q·f?=?80,921 GHz and τ _f ?=???8.21 ppm/°C, which are promising materials for the low temperature co-fired ceramics applications.     

The effects of CuO-doping on dielectric and piezoelectric properties of Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>–Ba(Zr,Ti)O<Subscript>3</Subscript> lead-free ceramics

CuO-doped lead-free ceramics based on bismuth sodium titanate (Bi_0.5Na_0.5TiO₃, BNT) and barium zirconate titanate (Ba(Zr_0.07Ti_0.93)O₃, BZT) were prepared via a multi-step solid-state reaction process. The BNT–BZT with CuO dopant ceramics sintered at 1150–1180 °C for 2 h in air showed a pure perovskite structure. SEM images reveal that a small amount of CuO (<2 mol%) play a significant role on the microstructure to improve its sintering attributes, while it will degrade when the dopant is added beyond 2 mol%. The dielectric and piezoelectric properties of CuO-doped BNT–BZT ceramics were evaluated. At room temperature, the sample doped with 2 mol% CuO shows quite good properties such as a high piezoelectric constant (d ₃₃ ∼156.5 pC/N) and a high electromechanical coupling factor (k _t ∼52%). The depolarization temperature increased dramatically and the maximum permittivity temperature decreased slightly.     

Synthesis,dielectric, and hysteresis behaviour of Ba(Nb<Subscript>0.2</Subscript>Ti<Subscript>0.8</Subscript>)O<Subscript>3</Subscript> ceramics and their solid solutions with BaZrO<Subscript>3</Subscript>

Solid state reaction technique was employed to synthesize Ba(Nb_0.2Ti_0.8)O₃ [BNT], and 0.9Ba(Nb_0.2Ti_0.8)O₃ + 0.1BaZrO₃ [BNT + BZ] samples. Sintered pellets were investigated for its dielectric (ε_r and tanδ) properties in the temperature range 100 K–380 K and in the frequency range of 100 Hz–1 MHz. The variation of ε_r and tan δ may be attributed to hopping of trapped charge carriers, which resulted in an extra dielectric response in addition to the dipole response. Hysteresis loop measurements were studied in the temperature regime 295 K–423 K. Loop area shrunk with the increase of temperature that may be due to phase transition from ferroelectric to paraelectric state.     

Synthesis of nanocrystalline TiO<Subscript>2</Subscript> by tartarate gel method

A gel was formed when a mixture of TiOCl₂ and tartaric acid was heated on a water bath. Ultrafine powders of TiO₂ in the anatase phase were formed, when the gel was decomposed at 623 K and the mole ratio of tartaric acid to titanium was 2. The anatase phase was converted into rutile phase on annealing at higher temperatures, > 773 K. When initial ratio of titanium to tartaric acid was < 2, the decomposition of gel leads to the formation of mixed phases of rutile and anatase. However, pure rutile phase was not formed by the decomposition of gel for any ratio of tartaric acid and titanium. These powders were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and surface area measurements. The average particle size obtained for anatase phase was 3 nm whereas it was 30 nm for rutile phase. Raman scattering experiments were also performed to confirm both anatase and rutile phases.     

Microstructures and dielectric properties of Y/Zn codoped BaTiO<Subscript>3</Subscript> ceramics

The microstructures and dielectric properties of Y/Zn codoped BaTiO₃ ceramics sintered in a reducing atmosphere were investigated. XRD analysis indicated the crystal structure of samples change from tetragonal to pseudocubic with increasing Y₂O₃ and ZnO content. SEM micrographs showed Y₂O₃ can suppress grain growth more effectively compared with ZnO, which is ascribed to the presence of second phase Y₂Ti₂O₇. Proper amount of Y₂O₃ and ZnO can significantly improve the dielectric temperature characteristics due to the formation of grain core-shell structure. The high performance dielectrics meeting the X7R code were achieved by codoping 1.5 mol% Y₂O₃ and 3.0 mol% ZnO.     

Structure and properties of Ba(Zr<Subscript>0.2</Subscript>Ti<Subscript>0.8</Subscript>)O<Subscript>3</Subscript> ceramics prepared by spark plasma sintering

Ba(Zr_0.2Ti_0.8)O₃ (BZT) ceramics are prepared from spray-dried powder by spark plasma sintering (SPS) and by normal sintering. By the application of SPS, ceramics with >96% relative densities could be obtained by sintering at 1,100 °C for 5 min in air atmosphere. The pellet as sintered by SPS at 1,100 °C was black and conductive. Although SPS was carried out in air atmosphere, the samples were deoxidized by heating the carbon die. By post-annealing at 1,000 °C for 12 h in air, the pellet was oxidized and became white and insulating. Grain growth was suppressed in the ceramics prepared by SPS, and the average grain size was 0.52 μm. The starting powder contained 1.90% carbon, mainly as binder, and the SPS-prepared ceramics and ordinary prepared ceramics contained 0.15 and 0.024% carbon, respectively. The BZT ceramics obtained by SPS and the subsequent annealing at 1,000 °C for 12 h exhibited a mild temperature dependence of their dielectric constant. The field-induced displacement of the BZT ceramics was less hysteretic and smaller than that of the ceramics sintered by the conventional method.